CN102660898A - Preparation method for highly-dispersed semi-crosslinked AKD (Alkyl Ketene Dimer) as neutral/alkali sizing agent - Google Patents
Preparation method for highly-dispersed semi-crosslinked AKD (Alkyl Ketene Dimer) as neutral/alkali sizing agent Download PDFInfo
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Abstract
The invention discloses a preparation method for highly-dispersed semi-crosslinked AKD (Alkyl Ketene Dimer) as a neutral/alkali sizing agent. The preparation method comprises the following steps of: firstly, degrading cassava starch under the action of fungal alpha-amylase and carrying out cationization on the degraded cassava starch with 3-chlorine-2-hydroxypropyl trimethyl ammonium chloride under the action of sodium hydroxide; secondly, neutralizing with acetic acid to obtain a cationic cassava starch solution; carrying out graft copolymerization reaction on the cationic cassava starch solution, butyl methacrylate, octadecyl methacrylate, hydroxyethyl methacrylate, acrylamide and methacryloyloxyethyl-trimethyl ammonium chloride under the action of ammonium persulfate to obtain a copolymer, wherein the copolymer contains a semi-crosslinked structure; and applying the semi-crosslinked structure as an emulsifying agent to emulsification of AKD and palm wax to obtain the highly-dispersed semi-crosslinked AKD as the neutral/alkali sizing agent. The emulsion particles of the prepared neutral/alkali sizing agent carry positive charges and have stronger emulsifying and dispersing capabilities; and when the sizing is carried out under the neutral/alkali conditions, the sizing degree is remarkably improved and favorable attaching property and sizing effect are obtained.
Description
Technical field
The invention belongs to polymer chemistry sizing agent technical field, among particularly a kind of high dispersive half crosslinked AKD/preparation method of alkaline sizing agent.
Background technology
The major progress of modern applying glue technology be in/popularization of alkaline bleach liquor sizing technology, during acid papermaking is converted into/alkaline paper-making is the great change on world's papermaking history.In/alkaline bleach liquor sizing is in papermaking process, the pH value is adjusted to more than 7, in principle without a kind of glue applying method of aluminum sulfate.In commonly used/alkaline sizing agent alkyl ketene dimer (being called for short AKD) is the product of phase late 1940s research and development; AKD be a kind of can with the response type of fibrin reaction in/alkaline sizing agent; It can be as internal sizing agent, again can be as Cypres.Its design feature is to be made up of active group and hydrophobic grouping; The fusing point of AKD is lower; Active group quaternary lactonic ring ability under the hot conditions of Dryer Section of Paper Machine in the molecule and the hydroxyl reaction on the cellulose form the beta-keto ester bond and are positioned on the fiber, and the hydrophobic group chain alkyl produces anti-water effect at fiber surface.Through among the AKD/alkaline bleach liquor sizing, the one way retention of paper whiteness, feel, WATER RESISTANCE, physical strength, printability, resistance to ag(e)ing and filler etc. all is significantly improved.And can to adopt cheap powdered whiting be filler, reduced content of harmful in the plain boiled water, improved the cyclic utilization rate of plain boiled water, and AKD is lower than the cost of acid accumulator size simultaneously.Adopt AKD carry out in/alkaline bleach liquor sizing can improve paper product quality and price, cut down the consumption of energy, improve environmental pollution and paper machine operation performance etc.; Therefore can obtain tangible economic benefit and social benefit, increasing papermaking enterprise is recognized and is used among the AKD/superiority and the necessity of alkaline sizing agent.China's paper making raw material is main with straw pulp, timber resource shortage, and the secondary stock consumption increases, in the utilization/the alkaline bleach liquor sizing technology has realistic meaning.Follow among the AKD/the alkaline bleach liquor sizing technology progressively enlarges in China's Application Areas; Technology is increasingly mature; In/benefit of alkaline paper-making progressively obtains embodying; Accelerated paper industry by acid papermaking in/trend that alkaline paper-making changes, in recent years AKD become domestic paper plant use at most, the most ripe, the most effectively in/alkaline sizing agent.
Among the AKD/alkaline bleach liquor sizing gives paper some excellent properties, and its weak point is also arranged simultaneously.Rate of charge during according to reaction can know to have only few part A KD that esterification has taken place, and most of AKD is retained in first reactor as blend components, does not play the effect of sizing agent.The research that improves in recent years and improve the AKD emulsion property is active day by day; Improve the reactivity and the sizing efficiency of AKD emulsion; Exploitation and production have well emulsify and dispersibility, can be that China's papermaking researcher is made great efforts the problem studied always with the AKD emulsion that the AKD that does not participate in reaction carries out effective emulsification and dispersion.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art; The object of the present invention is to provide among a kind of high dispersive half crosslinked AKD/preparation method of alkaline sizing agent; In the gained/alkaline sizing agent has the good emulsifying dispersibility; Can the AKD that not participate in reaction be carried out fully emulsified and effective dispersion, thereby improve the reaction efficiency and the sizing efficiency of sizing material.
For achieving the above object, the technical scheme that the present invention adopts is:
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, comprise following concrete steps:
The first step added in first reactor 50-55 ℃ the time reaction 1.0-2.0 hour with water, tapioca and fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add NaOH then, be warmed up to 60-70 ℃ and add 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1.0-2.0 hour again; Be cooled to 50-55 ℃ and add acetic acid; Reduce to 20-30 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with butyl methacrylate, octadecyl methacrylate and hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with acrylamide, methylacryoyloxyethyl trimethyl ammonium chloride and water by 7: 4: 20 mass ratio,
The 4th step, ammonium persulfate and water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 65-70 ℃; Add ammonium persulfate aqueous solution, first mix monomer and second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.0-2.0 hour
In the 6th step, room temperature was reduced to then in 85-90 ℃ of insulation reaction 3.0-3.5 hour in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added AKD emulsifying agent, palm wax and AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 85-90 ℃; After treating palm wax and AKD fusion, stirred 40-50 minute, the hot water that under agitation adds 85-90 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25-30MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5-8.5, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 5.0-7.5Kg/t paper, the Cobb value of newsprint is 35-40g/m after the applying glue
2, tensile index 55-60 Nm/g, tear index are 7.7-8.2 mNm
2/ g, and save sizing material 25-30%.
The present invention is earlier with tapioca degraded carrying out then cationization; Carry out graft copolymerization with acrylic acid ester again; Containing half cross-linked structure in the copolymer molecule that obtains, itself is exactly the sizing agent of excellent performance, and it is applied to the emulsification of AKD and palm wax as emulsifying agent; In the preparation/the alkaline sizing agent emulsion particle has positive charge; Have stronger emulsification and dispersibility, can the AKD that not participate in reaction be carried out effective emulsification and dispersion, obtain sizing agent emulsion stable, good fluidity.In/when carrying out applying glue under the alkali condition; The sizing agent that adds is dispersed between the fiber; And and fiber-reactive, the arrangement that makes fiber is more closely, distributing becomes very evenly, and the terminal AKD that introduces of fiber molecule can significantly reduce its surface energy; Degree of sizing obviously improves, and has good retention and sizing efficiency.
The specific embodiment
To be described in further detail the present invention with specific embodiment below.
Embodiment one
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 50 ℃ the time reaction 1.0 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2.0 hours again; Be cooled to 50 ℃ and add 7 gram acetic acid; Reduce to 20 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 65 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.0 hours
In the 6th step, room temperature is reduced to then in 85 ℃ of insulation reaction 3.5 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 85 ℃; After treating palm wax and AKD fusion, stirred 50 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.5, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 5.0Kg/t paper, the Cobb value of newsprint is 40 g/m after the applying glue
2, tensile index 55 Nm/g, tear index are 7.7 mNm
2/ g, and save sizing material 30%.
Embodiment two
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 51 ℃ the time reaction 1.2 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours again; Be cooled to 51 ℃ and add 7 gram acetic acid; Reduce to 22 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 66 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.2 hours
In the 6th step, room temperature is reduced to then in 86 ℃ of insulation reaction 3.4 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 86 ℃; After treating palm wax and AKD fusion, stirred 48 minutes, the hot water that under agitation adds 86 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 26MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.7, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 5.5Kg/t paper, the Cobb value of newsprint is 39 g/m after the applying glue
2, tensile index 56 Nm/g, tear index are 7.8 mNm
2/ g, and save sizing material 29%.
Embodiment three
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 52 ℃ the time reaction 1.4 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours again; Be cooled to 52 ℃ and add 7 gram acetic acid; Reduce to 24 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 67 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.4 hours
In the 6th step, room temperature is reduced to then in 87 ℃ of insulation reaction 3.3 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 87 ℃; After treating palm wax and AKD fusion, stirred 46 minutes, the hot water that under agitation adds 87 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 27MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 7.9, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 6.0Kg/t paper, the Cobb value of newsprint is 38 g/m after the applying glue
2, tensile index 57 Nm/g, tear index are 7.9 mNm
2/ g, and save sizing material 28%.
Embodiment four
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 53 ℃ the time reaction 1.6 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours again; Be cooled to 53 ℃ and add 7 gram acetic acid; Reduce to 26 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 68 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.6 hours
In the 6th step, room temperature is reduced to then in 88 ℃ of insulation reaction 3.2 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 88 ℃; After treating palm wax and AKD fusion, stirred 44 minutes, the hot water that under agitation adds 88 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 28MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.1, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 6.5Kg/t paper, the Cobb value of newsprint is 37 g/m after the applying glue
2, tensile index 58 Nm/g, tear index are 8.0 mNm
2/ g, and save sizing material 27%.
Embodiment five
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 54 ℃ the time reaction 1.8 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours again; Be cooled to 54 ℃ and add 7 gram acetic acid; Reduce to 28 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 69 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.8 hours
In the 6th step, room temperature is reduced to then in 89 ℃ of insulation reaction 3.1 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 89 ℃; After treating palm wax and AKD fusion, stirred 42 minutes, the hot water that under agitation adds 89 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 29MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.3, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 7.0Kg/t paper, the Cobb value of newsprint is 36 g/m after the applying glue
2, tensile index 59 Nm/g, tear index are 8.1 mNm
2/ g, and save sizing material 26%.
Embodiment six
Among a kind of high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, specifically may further comprise the steps:
The first step added in first reactor 55 ℃ the time reaction 2.0 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1.0 hours again; Be cooled to 55 ℃ and add 7 gram acetic acid; Reduce to 30 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 70 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 2.0 hours
In the 6th step, room temperature is reduced to then in 90 ℃ of insulation reaction 3.0 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 90 ℃; After treating palm wax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 90 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 30MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
With among this high dispersive half crosslinked AKD/alkaline sizing agent is used for 47g/m
2In the plasm-glue-blending of newsprint, the pH value is 8.5, among the high dispersive half crosslinked AKD/alkaline sizing agent consumption 7.5Kg/t paper, the Cobb value of newsprint is 35 g/m after the applying glue
2, tensile index 60 Nm/g, tear index are 8.2 mNm
2/ g, and save sizing material 25%.
In sum; The present invention carries out cationization after adopting the tapioca degraded, carries out graft copolymerization with acrylic acid ester again, contains half cross-linked structure in the copolymer molecule that obtains; It itself is exactly the sizing agent of excellent performance; It is applied to the emulsification of AKD and palm wax as emulsifying agent, in the preparation/the alkaline sizing agent emulsion particle has positive charge, has stronger emulsification and dispersibility; Can the AKD that not participate in reaction be carried out effective emulsification and dispersion, obtain sizing agent emulsion stable, good fluidity.In/when carrying out applying glue under the alkali condition; The sizing agent that adds is dispersed between the fiber; And and fiber-reactive, make fiber alignment more closely, distributing becomes very evenly, the terminal AKD that introduces of fiber molecule can significantly reduce its surface energy; Degree of sizing obviously improves, and has good retention and sizing efficiency.
Claims (7)
1. among a high dispersive half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, comprise following concrete steps:
The first step added in first reactor 50-55 ℃ the time reaction 1.0-2.0 hour with water, tapioca and fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add NaOH then, be warmed up to 60-70 ℃ and add 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride, be warming up to 90-95 ℃ of reaction 1.0-2.0 hour again; Be cooled to 50-55 ℃ and add acetic acid; Reduce to 20-30 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with butyl methacrylate, octadecyl methacrylate and hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with acrylamide, methylacryoyloxyethyl trimethyl ammonium chloride and water by 7: 4: 20 mass ratio,
The 4th step, ammonium persulfate and water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add cation cassava starch solution and water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 65-70 ℃; Add ammonium persulfate aqueous solution, first mix monomer and second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.0-2.0 hour
In the 6th step, room temperature was reduced to then in 85-90 ℃ of insulation reaction 3.0-3.5 hour in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added AKD emulsifying agent, palm wax and AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 85-90 ℃; After treating palm wax and AKD fusion, stirred 40-50 minute, the hot water that under agitation adds 85-90 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25-30MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
2. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 50 ℃ the time reaction 1.0 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 60 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 90 ℃ of reactions 2.0 hours again; Be cooled to 50 ℃ and add 7 gram acetic acid; Reduce to 20 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 65 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.0 hours
In the 6th step, room temperature is reduced to then in 85 ℃ of insulation reaction 3.5 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 85 ℃; After treating palm wax and AKD fusion, stirred 50 minutes, the hot water that under agitation adds 85 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 25MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
3. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 51 ℃ the time reaction 1.2 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 62 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 91 ℃ of reactions 1.8 hours again; Be cooled to 51 ℃ and add 7 gram acetic acid; Reduce to 22 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 66 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.2 hours
In the 6th step, room temperature is reduced to then in 86 ℃ of insulation reaction 3.4 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 86 ℃; After treating palm wax and AKD fusion, stirred 48 minutes, the hot water that under agitation adds 86 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 26MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
4. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 52 ℃ the time reaction 1.4 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 64 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 92 ℃ of reactions 1.6 hours again; Be cooled to 52 ℃ and add 7 gram acetic acid; Reduce to 24 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 67 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.4 hours
In the 6th step, room temperature is reduced to then in 87 ℃ of insulation reaction 3.3 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 87 ℃; After treating palm wax and AKD fusion, stirred 46 minutes, the hot water that under agitation adds 87 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 27MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
5. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 53 ℃ the time reaction 1.6 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 66 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 93 ℃ of reactions 1.4 hours again; Be cooled to 53 ℃ and add 7 gram acetic acid; Reduce to 26 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 68 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.6 hours
In the 6th step, room temperature is reduced to then in 88 ℃ of insulation reaction 3.2 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 88 ℃; After treating palm wax and AKD fusion, stirred 44 minutes, the hot water that under agitation adds 88 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 28MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
6. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 54 ℃ the time reaction 1.8 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 68 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 94 ℃ of reactions 1.2 hours again; Be cooled to 54 ℃ and add 7 gram acetic acid; Reduce to 28 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 69 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 1.8 hours
In the 6th step, room temperature is reduced to then in 89 ℃ of insulation reaction 3.1 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 89 ℃; After treating palm wax and AKD fusion, stirred 42 minutes, the hot water that under agitation adds 89 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 29MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
7. among a kind of high dispersive according to claim 1 half crosslinked AKD/and the preparation method of alkaline sizing agent, it is characterized in that, specifically may further comprise the steps:
The first step added in first reactor 55 ℃ the time reaction 2.0 hours with 200 gram water, 100 gram tapiocas and 0.6 gram fungal alpha-amylase, obtained degrading cassava starch; The mass ratio of water, tapioca and fungal alpha-amylase is 200: 100: 0.6; Add 10 gram NaOH then, be warmed up to 70 ℃ and add 70 gram 3-chloro-2-hydroxypropyl-trimethyl ammonium chlorides, be warming up to 95 ℃ of reactions 1.0 hours again; Be cooled to 55 ℃ and add 7 gram acetic acid; Reduce to 30 ℃ again, the mass ratio of tapioca, NaOH, 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride and acetic acid is 100: 10: 70: 7, and in first reactor, add water and regulate solid content to 25%; Promptly get cation cassava starch solution
Second step was mixed and made into first mix monomer with 10 gram butyl methacrylates, 18 gram octadecyl methacrylates and 1 gram hydroxyethyl methacrylate by 10: 18: 1 mass ratio,
The 3rd step was mixed and made into second mix monomer with 7 gram acrylamides, 4 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 20 gram water by 7: 4: 20 mass ratio,
The 4th step, 1 gram ammonium persulfate and 20 gram water are processed ammonium persulfate aqueous solution with mass ratio at 1: 20,
The 5th step; In second reactor, add 80 gram cation cassava starch solution and 79 gram water, the mass ratio of cation cassava starch solution and water is 80: 79, is warming up to 70 ℃; Add 21 gram ammonium persulfate aqueous solutions, 29 gram first mix monomers and 31 grams, second mix monomer simultaneously; The mass ratio of cation cassava starch solution, ammonium persulfate aqueous solution, first mix monomer and second mix monomer is 80: 21: 29: 31, and the whole charging time is 2.0 hours
In the 6th step, room temperature is reduced to then in 90 ℃ of insulation reaction 3.0 hours in the reinforced back that finishes, and with 120 order net filtrations, discharging obtains the AKD emulsifying agent,
The 7th step added 140 gram AKD emulsifying agents, 120 gram palm waxs and 140 gram AKD in the 3rd reactor, wherein the mass ratio of AKD emulsifying agent, palm wax and AKD is 140: 120: 140; Be warming up to 90 ℃; After treating palm wax and AKD fusion, stirred 40 minutes, the hot water that under agitation adds 90 ℃ is regulated solid content to 12.5%; Make cation cassava starch AKD meta emulsion; The meta emulsion behind the 30MPa homogeneous, is cooled to room temperature, obtains solid content and be among the 12.5% stable high dispersive half crosslinked AKD/alkaline sizing agent.
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| CN105732829A (en) * | 2016-02-23 | 2016-07-06 | 山东沛泽生物科技有限公司 | Starch essence |
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| CN105732829A (en) * | 2016-02-23 | 2016-07-06 | 山东沛泽生物科技有限公司 | Starch essence |
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